Plant seed compositions

ABSTRACT

Plant seeds are beneficiated by contacting them with an aqueous solution of a urea-sulfuric acid component containing the monourea adduct of sulfuric acid. The molar ratio of urea to sulfuric acid in the aqueous solution is preferably within the range of about 1/4 to about 7/4 so that at least about 25 percent of the sulfuric acid is present in the solution as the monourea adduct. The treatment of plant seeds with the aqueous urea-sulfuric acid components is particularly useful for removing residual plant matter from plant seeds, scarifying and improving the germination of plant seeds, and improving the processability and digestibility of plant seeds. Improvements in processability result from softened seed hulls or husks, improved extractability of oil from oil-containing seeds, and improved quality of treated seeds for the manufacture of seed derived products, particularly for the manufacture of grain-derived products. Compositions which involve mixtures of plant seeds and the urea-sulfuric acid components are also provided.

OF THE INVENTION

1. Field of the Invention

This invention relates to the treatment of plant seeds and, tocompositions for use in such methods, in particular, it relates tomethods and compositions useful for cleaning, scarifying, and improvingthe germination rate processability of plant seeds.

2. Description of the Art

Seeds of essentially all varieties are often treated by one or moreprocedures to improve their quality and utility for a variety of usessuch as storage, planting, oil-extraction, and subsequent processing forthe manufacture of seed-derived products such as animal foods, includinghuman foods. Although most seeds are treated after harvest, some aretreated before harvest by the application of chemicals maturation orthat facilitate harvesting or that promote maturation or that facilitateharvesting or accelerate germination.

Residual mineral and organic matter, particularly residual plant matterwhich is not an integral part of the seed husk or hull, is most oftenremoved from seeds intended for storage or subsequent use. The presenceof such residual organic matter interferes with handling apparatus andprocedures, promotes spoilage through the growth of bacteria and fungus,fouls the extraction products from certain seeds such as oils fromcotton seeds and the like, and can inhibit germination in seeds that arereplanted.

Current procedures for the removal of residual plant matter and otherorganic and/or mineral matter from plant seeds include washing withwater or other solutions, mechanical abrasion, and treatment at elevatedtemperatures with strong base such as calcium hydroxide, sodiumhydroxide, and the like. Seeds that are intended for replanting areoften treated to improve their germination rate, i.e., to reduce thetime required for seed germination after planting. Current practices forincreasing germination rate involve scarifying the seeds, bymechanically scraping or chemically treating the seed husk to increaseits permeability to moisture. Treatment with strong base increases thepermeability of the seed covering (which consists principally ofcellulose and lignand) by partially dissolving or modifying the seedcovering. Increased germination rate minimize disease or parasiteinfestation prior to germination and often facilitates better timing ofcrop emergence and maturation.

Similar mechanical and caustic treating procedures are employed to cleanand/or beneficiate seeds prior to extraction of oil or other seedproducts. Such treatments reduce the amount of energy required torecover oil from seeds by compression and/or increase the rate at whichsuch oils are extracted. Plant seeds also are processed to improve theirvalue as food for domestic animals and for the manufacture of (1)processed foods such as processed rice, wheat and other grains, (2)foods that require less cooking time for their preparation, (3) otherseed-derived food products such as cereals, bakery products, flour, cornmeal, etc., and (4) certain seed-derived vegetable products such as cornsyrup, and soy bean meal and other vegetable protein concentrates.

Contemporary mechanical seed-treating methods such as mechanicalscarification involve the use of relatively complicated equipment andthe expenditure of mechanical energy. They do not always result in equalor homogeneous scarification and/or cleaning of all seeds and thus canproduce a heterogeneous product. Furthermore, the necessity for complexmechanical equipment requires that the raw seeds be shipped to alocation at which such equipment is available. The chemical treatingmethods such as hot caustic treatment involve the use of substantialamounts of caustic reactants which are often consumed in the process.Such methods also require elevated temperatures, and thus excessiveenergy input, and relatively long contact times.

It is known that sulfuric acid will chemically react with vegetablematter. However, sulfuric acid is such a strong oxidizing andsulfonating agent that it cannot be employed for seed treatment withoutalso oxidizing and/or sulfonating desirable portions of the seedproduct.

Combinations of urea and sulfuric acid are also known and have been usedin the agricultural industry primarily when the simultaneous addition ofurea and sulfur to the soil is desired. It is also known that urea andsulfuric acid will combine to form adducts including themonourea-sulfuric acid adduct and the diurea-sulfuric acid adduct. Forinstance, D. F. du Toit, Verslag Akad. Wetenschsppen, 22, 573-4(abstracted in Chemical Abstracts, 8, 2346, 1914) disclosed that ureaforms certain compounds with oxalic, acetic hydrochloric, nitric andsulfuric acids. L. H. Dalman, "Ternary Systems of Urea and Acid. I.Urea, Nitric Acid and Water. II. Urea, Sulfuric Acid and Water. III.Urea, Oxalic Acid and Water"; JACS, 56, 549-53 (1934), disclosed thephase relationships between the solid phase and saturated solutionscontaining urea and sulfuric acid at 10° C. and 25° C. The SulfurInstitute, Sulfur Institute Bulletin No. 10 (1964), "Adding PlantNutrient Sulfur to Fertilizer", disclosed that urea reacts with sulfuricacid to form two complexes of "urea sulfate" which are usefulfertilizers. Methods of manufacturing certain combinations of urea andsulfuric acid are disclosed by Verdegaal et al. in U.S. Pat. No.4,310,343 and by Jones in U.S. Pat. No. 4,116,664. However, neitherthese nor other investigators recognized that urea-sulfuric acidcompositions containing a significant proportion of the monourea adductof sulfuric acid are uniquely active toward organic materials such asresidual organic matter contained on plant seeds and the husks or hullsof the plant seeds, or that the diurea adduct of sulfuric acid exhibitslittle, if any, of such activity.

Accordingly, a need exists for improved processes for treating plantseeds, and particularly for improved processes for cleaning and/orscarifying plant seeds, for increasing the germination rate of plantseeds, and for improving the quality of plant seeds for use in themanufacture of seed-derived products such as vegetable oils, vegetableprotein concentrates, and food products.

It is therefore a principal object of this invention to provide novelmethods for treating plant seeds.

Another object of this invention is the provision of methods forcleaning plant seeds.

Yet another object of this invention is the provision of methods forscarifying seeds.

Another object is the provision of methods for increasing thegermination rate of plant seeds.

Yet another object of this invention is the provision of methods forimproving the storage-stability of plant seeds.

Yet another object of this invention is the provision of methods forimproving the quality of plant seeds for the manufacture of seed-derivedproducts.

Another object is a provision of methods for improving theoil-extractability of oil-containing plant seeds.

Yet another object is the provision of methods for improving theprocessability of plant seeds for the manufacture of food products.

Another object is the provision of methods of extracting oil fromoil-containing plant seeds.

Yet another object of the provision of novel seedcontainingcompositions.

Another object is the provision of seed-containing compositions suitablefor use in the manufacture of improved plant seeds.

Yet another object is the provision containing compositions suitable foruse in the manufacture of see-derived products such as vegetable oil andfood products.

Other objects, aspects and advantages of this invention will be apparentto one skilled in the art in view of the following disclosure, thedrawing and the appended claims.

SUMMARY OF THE INVENTION

Briefly, the invention provides (1) methods for treating plant seeds,(2) seed-containing compositions useful in such methods, and (3) methodsof producing plant seed-derived products such as vegetable oils,vegetable protein concentrates, and other food products.

The novel methods of this invention involve contacting plant seeds withan aqueous solution containing urea and sulfuric acid, and optionally, asurfactant, in which solution the molar ratio of urea to sulfuric acidis within the range of about 1/4 to about 7/4. Within this range ofmolar ratios, at least about 25 percent of the sulfuric acid present inthe solution is in the form of the monourea adduct of sulfuric acid. Themonourea-sulfuric acid adduct is the component of the urea-sulfuric acidsolutions which is most active for the treatment of plant seeds. Themethods of this invention enable the accomplishment of one or more of avariety of objectives depending upon the types of plant seed treated,the condition of the plant seed before treatment, and the treatingconditions, the most important of which are the concentration and dosagerate of the urea-sulfuric acid solution, and treatment temperatures andcontact times. For instance, seeds can be cleaned of residual matterwhich is not an integral part of the seed or seed husk or hull underrelatively mild treatment conditions while more severe conditions arerequired to significantly change the thickness or permeability of theseed husk or hull. In contrast, the seed husk or hull can be partiallyor completely removed by the use of more severe treatment conditionsincluding higher dosage rates of the active monourea-sulfuric acidadduct, higher contacting temperatures, and longer contact times. Thus,the methods of this invention can be employed to (1) clean plant seedsof residual organic and/or mineral matter including residual plantmatter, (2) scarify or otherwise reduce the thickness of and/or increasethe moisture permeability of the seed hull or husk, (3) increase seedgermination rate, (4) improve seed storageability and resistance tobacterial and fungus infestation, (5) significantly reduce the thicknessand physical strength of the seed hull or husk and/or (6) partiallyhydrolyze the seed hull, husk or the seed itself, and thereby improvethe processability of the seeds for the manufacture of seed-derivedproducts such as vegetable oils, animal foods, and food products. Themethods of this invention are particularly useful for the removal ofresidual plant matter from raw seeds, such as the removal of lint fromcotton seeds, and for improving seed germination rate and processabilityfor the manufacture of products derived from seeds of essentially allplant varieties. These methods are also particularly useful for thebeneficiation of seeds which have relatively hard, impervious husks orhulls.

The novel compositions of this invention involve mixtures of plant seedsand the urea-sulfuric acid components useful in the methods of thisinvention, which may optionally contain a surfactant. These mixturesusually involve combinations of aqueous solutions of urea and sulfuricacid in which the molar ratio of urea to sulfuric acid is within therange of about 1/4 to about 7/4 dispersed over the seed's outer surfaceor in which the seeds to be treated are immersed. The urea and sulfuricacid, in combination, constitute at least about 0.5 weight percent ofthe novel compositions of this invention based on the weight of thetreated plant seeds.

The methods and compositions of this invention minimize or eliminatemany of the deficiencies associated with seed-treating processespresently available to the art. The described methods and compositionseliminate the need for complicated mechanical equipment such as thatpresently employed to clean, scarify and/or otherwise convert plantseeds for subsequent processing. They also eliminate need for the use ofsevere caustic treating processes and the relatively high energy demandsassociated with such processes. The urea-sulfuric acid componentsemployed in the methods and compositions of this invention arerelatively non-corrosive to both equipment and human skin and thus, aremore easily handled than are caustics or sulfuric acid. Furthermore, theurea-sulfuric acid components, do not degrade desirable portions of theplant seed; such degradation almost unavoidably occurs from the use ofsulfuric acid. These methods and compositions do not result in theaddition of any toxic components to plant seeds and thus do notintroduce toxic materials into seed-derived products. On the contrary,the urea-sulfuric acid components can be neutralized with base followingcontacting with the plant seeds to form compositions that containnutrient nitrogen (from urea) and nutrient sulfur (from sulfuric acid),both of which are beneficial to seed-derived products such as animalfeeds. Since the preferred urea-sulfuric acid components employed inthis invention do not contain decomposition products of urea and/orsulfuric acid, such as sulfamic acid and ammonium sulfamate, they do notintroduce such toxic materials into the seeds or into vegetable oils,food products, or other seed-derived products produced from the treatedseeds.

DETAILED DESCRIPTION OF THE INVENTION

This invention provides novel methods for (1) cleaning and otherwiseremoving residual organic and inorganic matter from plant seeds, (2)scarifying plant seeds by reducing the thickness and increasing themoisture permeability of the seed hull or husk, (3) increasing thegermination rate of plant seeds, (4) improving seed storage-stabilityand resistance to bacteria and fungus, and (5) improving the processingcharacteristics of plant seeds which are to be used for the manufactureof seed-derived products including vegetable oils, vegetable proteinconcentrates, starches, sugars, and fruit products, by at leastpartially hydrolyzing the hull and/or seed. Novel seed-containingcompositions which are particularly useful in the methods of thisinvention are also provided.

The seed-treating methods of this invention involve contacting plantseeds with a urea-sulfuric acid component which preferably comprises anaqueous solution of urea and sulfuric acid in which the molar ratio ofurea to sulfuric acid is within the range of about 1/4 to about 7/4. Theurea-sulfuric acid components contain an active amount of the monoureaadduct of sulfuric acid and, within the range of molar ratios referredto above, at least about 25 percent of the sulfuric acid is present asthe monourea-sulfuric acid adduct. The urea-sulfuric acid components maycontain any one of a variety of other materials and, in particular, theymay contain a surfactant. Surfactants increase the activity of theurea-sulfuric acid component toward seeds and other plant materials thatcontain lipophilic components such as fats, oils, waxes and otherhydrophobic substances.

The novel seed-containing compositions of this invention involvemixtures of plant seeds and the urea-sulfuric acid components useful inthe methods of this invention, with or without a surfactant. Suchseed-containing compositions usually contain an amount of theurea-sulfuric acid component such that the urea and sulfuric acid, incombination, constitute at least about 0.5 weight percent of thecomposition.

Plant seeds which may be treated in accordance with the methods of thisinvention and/or which may constitute components of the novelseed-containing compositions of this invention include seeds of allseed-producing plants including all perennial and annual, coniferous anddeciduous plants including trees, shrubs, vines, and grasses. Themethods and compositions of this invention are particularly useful forthe treatment of the seeds of such plants which are employed forornamental, fruit-bearing, fiber producing and vegetable producingpurposes, in addition to food and ornamental grasses, and of plants suchas certain varieties of sunflower and cotton, the seeds of which areused in the production of oil and other seed-derived products.Illustrative food crops include grain crops such as wheat, barley, oats,corn, rice, and the like; vegetables such as carrots, lettuce, celery,artichokes and all varieties of peas, beans, and the like; and fruitcrops such as berries, including blackberries, boysenberries, etc.,cherries, avocadoes, pears, apples, citrus, etc. Illustrative grasscrops include the various varieties of grass grown for hay includingbermuda grass and alfalfa, and ornamental grasses such as Kentuckybluegrass, ryegrass, and the like. Illustrative of other ornamentalplants are flowering plants such as azaleas, chrysanthemums, marigolds,and decorative vines such as mock strawberry and iceplant. Illustrativeoil-producing plant seeds are the seeds of plants from which oils usefulin foods or other products can be derived. Such products include foodproducts, cooking oils, components of varnishes, soaps, drying oils forpaints, waxy oils for waterproofing paper, and the like. Such seed oilsare usually derived by expression (pressing) or solvent extraction ofthe raw or partially processed seeds of plants such as Helianthus annus(sunflower oil); safflower (carthamus) seeds which produce saffloweroil; flax seed (Linum usitatissimum) from which linseed (flax seed) oilis derived; cotton; peanuts; perilla ocimaides from which perilla oil, asubstitute for linseed oil, can be derived; seeds of the oiticica tree(Licania rigida) from which oiticica oil is derived; and seeds ofAleurites cordata used to produce Tung oil; and others.

The urea-sulfuric acid components employed in the methods andcompositions of this invention are reaction products of urea andsulfuric acid in which the molar ratio of urea to sulfuric acid iswithin the range of about 1/4 to about 7/4. In such components, at leastabout 25 percent of the sulfuric acid is present as themonourea-sulfuric acid adduct. These components may be employed in themethods disclosed herein, as melts or as solutions of such mixtures inwater or other solvents, and they may contain other components such assurfactants which do not substantially negate the activity of theurea-sulfuric acid component.

The urea-sulfuric acid components may also contain unreacted (free)sulfuric acid or the diurea adduct of sulfuric acid. The useful andpreferred proportions of urea, sulfuric acid, and of the mono- anddiurea adducts of sulfuric acid, relative to each other, can beconveniently expressed in terms of the urea/sulfuric acid molar ratio.This ratio will usually be within the range of about 1/4 to about 7/4,preferably about 1/2 to about 3/2, and most preferably between about 1/1to about 3/2. Urea/sulfuric acid molar ratios within the range of about1/4 to about 7/4 define compositions in which at least 25 percent of thesulfuric acid is present as the monourea sulfuric acid adduct. Molarratios within the range of 1/2 to about 3/2 define compositions in whichat least 50 percent of the sulfuric acid is present as the monoureaadduct. The most preferred molar ratio range of about 1/1 to about 3/2defines compositions which contain essentially no uncomplexed sulfuricacid and in which at least 50 percent of the sulfuric acid is present asthe monourea-sulfuric acid adduct. The most preferred combinations haveurea/sulfuric acid molar ratios of about 1/1. In such compositions,essentially all of the sulfuric acid is present as the monourea-sulfuricacid adduct and such compositions are essentially free of uncomplexedsulfuric acid. Substantial amounts of uncomplexed sulfuric acid, i.e.,sulfuric acid that is not complexed with urea as either the mono- ordiurea adduct, are unpreferred since sulfuric acid, when present insubstantial amounts, may promote reactions such as oxidation,sulfonation and/or other reactions. While excess urea is generally notdetrimental to the performance of the urea-sulfuric acid components, thepresence of excess urea above the amount required for a urea/sulfuricacid molar ratio of 1/1, results in the conversion of a portion of themonourea-sulfuric acid adduct to the diurea adduct which has little orno activity for beneficiating plant seeds in accordance with thisinvention. In fact, compositions in which a large percentage of thesulfuric acid is combined as the diurea adduct (such as 28-0-0-9 whichcontains only the diurea adduct and excess urea) can inhibit or evendestroy the germinating ability of plant seeds. Thus, the preferredurea-sulfuric acid components are those in which at least about 75,usually at least about 85, and most preferably at least about 90 percentof the sulfuric acid is present as the mono- and/or diurea-sulfuric acidadduct. Particularly preferred compositions are those that containessentially no free sulfuric acid; thus essentially 100 percent of thesulfuric acid would be combined with urea as the mono- and/or diureaadduct. Furthermore, since the monourea adduct is the most activecombined form of urea and sulfuric acid, and since the diurea adduct isundesirable, at least in these embodiments of this invention in whichpreservation of the seed-germinating ability is desired, at least about25, usually at least about 50, preferably at least about 70, and mostpreferably about 80 to about 100 percent of the sulfuric acid is presentas the monourea-sulfuric acid adduct.

The urea-sulfuric acid components can be produced by the reaction ofurea and sulfuric acid and, optionally water, by either batch orcontinuous processes. The more concentrated solutions, i.e., thosecontaining less than 25 weight percent, preferably less than 15 weightpercent water, are particularly preferred for purposes of manufacture,storage and shipment. Also, the urea-sulfuric acid component ispreferably substantially or completely free of decomposition products ofurea and/or sulfuric acid such as sulfamic acid, ammonium sulfamate,ammonium sulfate, etc., to assure that the preferred liquid and solidurea-sulfuric acid components employed in the methods and compositionsof this invention are also free of such decomposition products. Theabsence of decomposition products in the urea-sulfuric acid componentalso assures that the sulfuric acid activity of that component has notbeen degraded by decomposition. Sulfuric acid decomposition also reducesthe amount of acid in the urea-sulfuric acid component available tocombine with the urea to form the active monourea-sulfuric acid adduct.

Urea-sulfuric acid components free of decomposition products can beproduced by the reaction of solid urea and concentrated sulfuric acid bythe methods described in my copending application Ser. No. 318,629 filedNov. 5, 1981, now U.S. Pat. No. 4,445,925 the disclosure of which isincorporated herein by reference.

Solid urea-sulfuric acid components useful in producing the solutionsemployed in the methods of this invention can be obtained bycrystallization from their respective aqueous solutions, as described inmy copending application Ser. No. 444,667, "Methods for ControllingVegetation", filed Nov. 26, 1982, the disclosure of which isincorporated herein by reference. Surfactants or other components, whenpresent, will either crystallize at approximately the same temperatureas the urea-sulfuric acid component or will be entrained with thecrystallized urea-sulfuric acid component or will be entrained with thecrystallized urea-sulfuric acid component. In the alternative, thesurfactant and/or other components can be added, when desired, to thedry or damp urea-sulfuric acid component by any suitable mixingtechnique after crystallization of the urea-sulfuric acid component fromits solution.

As described in my copending application Ser. No. 444,667, theurea-sulfuric acid aqueous solution there referred to as 18-0-0-17 has acrystallization temperature of 50° F. Designations such as 18-0-0-17 areconventionally used in the agricultural industry to define the weightpercentages of nitrogen, phosphorus, potassium and a fourth component,in this case sulfur, contained in a composition. Thus, 18-0-0-17contains 18 weight percent nitrogen as urea, 0 percent phosphorus, 0percent potassium, and 17 weight percent sulfur. The 18-0-0-17 solutionhas a urea/sulfuric acid molar ratio of about 1.2 and contains about 90weight percent of a combination of urea and sulfuric acid. Urea andsulfuric acid, in combination, constitute 80 weight percent of theaqueous solution designated as 10-0-0-19 in copending application Ser.No. 444,667, which composition has a urea/sulfuric acid molar ratio ofabout 0.6 and which crystallizes at about 42° F. The aqueous solutiondesignated as 9-0-0-25 comprises approximately 96 weight percent of acombination of urea and sulfuric acid, has a urea/sulfuric acid molarratio of about 0.4, and crystallizes at 14° F. The indicatedcrystallization temperatures of the three urea-sulfuric acid aqueoussolutions referred to immediately above, and the crystallizationtemperatures for other formulations of urea and sulfuric acid useful inthe composition and methods of this invention, are illustrated, in part,by the isotherms in the ternary phase diagram for urea, sulfuric acidand water in the drawing accompanying copending application Ser. No.444,667. The crystallization temperatures for other urea-sulfuric acidcombinations useful in the compositions and method of this invention canbe determined from that drawing or by cooling the selected solutionuntil crystallization occurs. The crystallized material can be separatedfrom the supernant aqueous phase by any suitable solid-liquid separationtechnique such as filtration, centrifugation, decanting, and the like,and the recovered damp solid can be dried by evaporation if desired.

The aqueous solutions of the urea-sulfuric components useful in thetreatment of seeds in accordance with methods and compositions of thisinvention can be either concentrated or very dilute. Although themonourea adduct appears to dissociate to urea and sulfuric acid insolutions containing significantly less than about 0.5 weight percentcombined urea and sulfuric acid, the dissociated components canrecombine to form the active adduct on the treated seeds if water isallowed to evaporate.

However, very low urea-sulfuric acid component concentrations, e.g., 0.2percent, or less, generally do not allow for sufficient dosage rates ofthe active urea-sulfuric acid component in many instances. Thus, ureaand sulfuric acid, in combination, will usually constitute at leastabout 0.5, generally at least about 1, preferably at least about 5, andthe most preferably at least about 10 weight percent of the aqueoussolutions as applied to the seeds. Aqueous solutions containing higherconcentrations of the useful urea-sulfuric acid components, while moreactive, are also more viscous and are more difficult to apply evenly tothe treated seeds. With these factors in mind, the applied solution willusually contain about 0.5 to about 90, normally about 1 to about 90, andpreferably about 5 to about 80 weight percent urea and sulfuric acid ona combined weight basis.

The urea-sulfuric acid component-containing compositions employed in themethods of this invention may also contain one or more surfactants.Surfactants increase the activity of the urea-sulfuric acid componenttoward plant seeds, particularly toward seeds that contain and/or arecombined with lipophilic substances such as waxes, oils and otherhydrophobic substances. Surfactants also increase the wetting ability ofthe aqueous solutions useful in this invention and, thereby, improve thedistribution of such solutions over the seed surface.

The selected surfactant is preferably sufficiently chemically stable inthe presence of the urea-sulfuric acid component to assure that thesurfactant retains its wetting ability for the period of time requiredto manufacture, store, transport, and apply the composition. Thestability of any surfactant can be readily determined by adding anamount of the surfactant to the urea-sulfuric acid component-containingcomposition in which it is to be employed, and monitoring thecombination by conventional nuclear magnetic resonance (NMR) techniques.NMR can be used to monitor the frequency and magnitude of spectral peakscharacteristic of a selected nucleus, e.g., a hydrogen nucleus, in thesubject molecule, i.e., in the surfactant. Persistent spectral peakmagnitude and frequency over a period of 5 to 6 hours indicatestability. Diminished magnitude or a shift in peak frequency associatedwith the selected nucleus indicates instability, i.e., that thearrangement of functional groups in the surfactant molecule has beenmodified.

Illustrative of classes of stable surfactants are nonionics such as thealkylphenol polyethylene oxides, anionics such as the long chain alkylsulfates, and cationics such as 1-hydroxyethyl-2-heptadecenylgloxalidin. Of these, the polyethylene oxide nonionic surfactants areparticularly preferred. Illustrative of preferred specific surfactantsis the nonionic surfactant marketed by Thompson-Hayward, Inc., under thetrademark T-MULZ 891.

The surfactant concentration is preferably sufficient to increase thewetting ability of the aqueous solution for the plant seeds and willusually be at least about 0.05, generally at least about 0.1, andpreferably at least about 0.2 weight percent of the aqueous solution asapplied. Surfactant concentrations of about 0.2 to about 1 weightpercent are adequate in most applications. The concentration ofsurfactant in the solid urea-sulfuric acid components which also can beemployed in this invention should be sufficient to produce the desiredconcentration in the aqueous solution that is to be produced bydissolving the solid in water. For example, a solid urea-sulfuric acidcomponent that is to be dissolved to produce an aqueous solutioncontaining 5 weight percent of a combination of urea and sulfuric acidwould be diluted by a factor of 19 to 1 in order to produce thatsolution. Thus, the solid component should contain approximately 19times the surfactant concentration desired in the solution on a weightpercent basis. Hence, if a surfactant concentration of 0.1 weightpercent is desired in the final solution, the solid component shouldcontain approximately 1.9 weight percent of the surfactant.

The solid and liquid urea-sulfuric acid-containing compositions usefulin this invention may also contain other components such as foodadditives, solvents, plant seed processing aids such as organicsolvents, plant nutrients, biocides, plant growth regulants, etc., whichdo not neutralize the sulfuric acid contained in the urea-sulfuric acidcomponent, react with the urea-sulfuric acid component, or otherwisesubstantially inhibit the activity of the urea-sulfuric acid componenttoward the plant seeds.

The aqueous solutions employed in the methods of this invention can beproduced by any method capable of mixing the desired components toproduce a solution of the desired composition Thus, the surfactantand/or other components, when used, can be added to the concentratedurea-sulfuric acid solution during or immediately after its manufactureby the process described in my copending application Ser. No. 318,624,referred to above, or they can be added the solution with the plantseeds to be treated. Alternatively, the optional components can be mixedwith the amount of water required to produce a concentrated or diluteaqueous solution or concentrated aqueous urea-sulfuric acid component.Of course, dissolution of the solid compositions useful in thisinvention that contain both the urea-sulfuric acid component and thedesired optional components, in water, will also result in formation ofthe active aqueous compositions of this invention.

The methods of this invention involve contacting the plant seeds to betreated with an aqueous solution of the urea-sulfuric acid componentunder conditions of time, temperature, and dosage rate sufficient toaccomplish the desired degree of seed modification. The plant seeds canbe contacted with the aqueous urea-sulfuric acid component by any one ofseveral suitable methods which include spraying the seeds with theaqueous solutions, immersing the seeds in the solution, or dusting theseeds with the solid urea-sulfuric acid components and then contactingthe mixture with sufficient water to form the aqueous solution incontact with the plant seeds. Of course, the seeds can be dampened priorto application of the solid urea-sulfuric acid component. After thedesired degree of seed modification has been achieved, the seeds can beseparated from the aqueous urea-sulfuric acid component by filtering(when the seeds are immersed in the described solutions) or by washingwith water. Optionally, the urea-sulfuric acid component can beneutralized by mixing the treated plant seeds with an amount of basesuch as sodium hydroxide, calcium hydroxide, potassium hydroxide, etc.,sufficient to neutralize the sulfuric acid contained in theurea-sulfuric acid component. The neutralized urea-sulfuric acidcomponent can be retained as a component of the seed product or can bewashed from the seeds with water.

The plant seeds to be treated can be contacted with the aqueousurea-sulfuric acid components either prior to or after harvest. Thus,the aqueous urea-sulfuric acid components can be sprayed ontounharvested seeds in situ on the plant and the seeds can then beharvested or can be allowed to drop in place as desired. The methods ofthis invention can also be employed to treat partially processed plantseeds such as seeds that have already been cleaned of residual organicmatter, seeds which have been partially scarified by chemical ormechanical means, or which have been partially hydrolyzed by contactwith caustic as described above.

The contacting temperatures employed in the methods of this inventionshould be above the crystallization point of the aqueous urea-sulfuricacid component and below its thermal decomposition temperature which isapproximately 176° F. Thus, contacting temperatures will usually bewithin the range of about 32 to about 170° F., generally about 40 toabout 160° F., preferably about 60 to about 160° F. Contactingtemperatures of about 60 to about 90° F. are generally sufficient formost purposes. The rate at which seed modification occurs increases ascontacting temperature is increased. Thus, the rate at which residualplant matter is removed and at which seeds are scarified and/orhydrolyzed, increases as contacting temperature is increased.

The plant seeds should be contacted with the aqueous urea-sulfuric acidcomponents for a period of time sufficient to achieve the desired degreeof modification. Contact times will usually be at least about 1 minute,generally at least about 5 minutes, and preferably at least about 10minutes. Contact times in the range of about 1 minute to about 100 hoursare sufficient to achieve essentially all degrees of seed modificationdesired. Nevertheless, since the urea-sulfuric acid components remainactive indefinitely unless they are neutralized, contact times muchlonger than 100 hours may be employed if desired to achieve morecomplete conversion. The extent of seed modification, i.e., the extentof organic matter removal, scarification, and digestibility andprocessability improvement, increases as contact time is increased.

The dosage rate of the urea-sulfuric acid component may be varied over awide range and should be sufficient to accomplish the desired degree ofseed modification within the contact time and at the contact temperatureemployed. Generally, the amount of the aqueous solution applied shouldbe sufficient to cover a significant portion or all of the seed surfaceor should be sufficient to allow immersion of the seeds in the aqueoussolution when complete immersion is desired. The dosage rate of theurea-sulfuric acid component, expressed on a waterfree basis, willusually be at least about 0.5, usually at least about 1, and preferablyat least about 5 pounds of the combination of urea and sulfuric acid per100 pounds of treated seeds. When applied at these dosage rates, theurea and sulfuric acid, in combination, will constitute at least about0.5, generally at least about 1 and preferably at least about 5 weightpercent of the treated seeds.

Essentially all types of seed modification in accordance with thisinvention can be achieved at dosage rates within the range of about 0.5to about 200 pounds of the combination of urea and sulfuric acid per 100pounds of treated seeds. Of course, much higher dosage rates can beemployed to facilitate complete immersion of the plant seeds, continuousprocessing, and the like. The rate at which seed modification occursincreases with dosage rate of the urea-sulfuric acid component up to thepoint that the plant seed surfaces are completely wet with the aqueousurea-sulfuric acid component. The rate at which seed modification occursdoes not increase significantly past that point unless the seeds containbasic materials that neutralize a portion of the sulfuric acid in theurea-sulfuric acid component. In such instances, an excess of theurea-sulfuric acid component should be provided.

Contacting temperature, contact time, and dosage rate of theurea-sulfuric acid component can be correlated to achieve the desireddegree of seed modification. Thus, the plant seeds can be rapidlymodified by contacting them with a moderate dosage of the urea-sulfuricacid component, e.g., about 10 pounds of the combination of urea andsulfuric acid per 100 pounds of treated seeds, for a relatively shortcontact time of approximately 10 minutes, at an elevated temperature of150° F. A similar degree of modification can be achieved at the samedosage rate by employing a contacting temperature of 70° F. and a longercontact time. The optimum combination of contact temperature, time, anddosage rate, can best be determined by treating separate samples of theplant seeds at different dosage rates, contact temperatures and times,observing the extent of seed modification which occurs in each test, andselecting the combination of processing conditions best suited toaccomplish the desired degree of modification of the tested plant seeds.

Relatively mild contacting conditions are usually adequate to cleanplant seeds of residual organic matter. Thus, lint can be removed fromcotton seeds by treatment with sufficient 10-0-0-18 to completely wetthe seeds at 70° F. within approximately 20 minutes. Longer contacttimes can be employed without damage to the treated cotton seeds. Suchprocedures can be employed to remove residual organic matter of any typefrom all varieties of plant seeds. Thus, residual fruit matter can beremoved from fruit seeds such as peach pits, citrus seeds, grains andthe like. The cleaning of plant seeds by the methods of this inventionimproves their handling characteristics and reduces the likelihood ofspoilage during storage due to bacterial or fungus infestation.

Plant seeds can be scarified, and seed germination rate can be increasedby contacting the seeds with the urea-sulfuric acid component underrelatively mild conditions similar to those employed to remove residualorganic matter as discussed above. Scarification involves physical orchemical weakening and/or partial removal of the seed husk or hull.Germination rate is improved by increasing the permeability of the seedhusk or hull to moisture. Further improvements in both of thesecharacteristics can be achieved by treating the plant seeds undersomewhat more severe conditions, i.e., for longer contact times, athigher temperature and/or with higher dosage rates of the urea-sulfuricacid component. However, it is generally preferable to avoid completelypenetrating and/or removing the seed husk or hull if the seeds are to bereplanted, since even the scarified seed husk protects the seed againstdisease and parasites. Thus, the treatment conditions employed toimprove the germination rate of plant seeds should not be so extremethat they destroy the seeds viability, i.e., its ability to germinate.Seed viability and the extent of improvement in germination rate can bedetermined by any one of several procedures known in the art. Forinstance, the germination rate and viability of seed samples treatedunder different conditions of time, temperature and/or dosage rate, canbe readily evaluated by the so-called "wet towel" germination andviability test. In accordance with this test several treated seeds areplaced on a moist paper or cloth towel and are maintained at atemperature of approximately 90° F. for a period of time sufficient toallow germination. The absence of germination indicates that seedviability has been impaired. In the alternative, samples of the seedstreated under different conditions can be planted, either in thegreenhouse or in field plots, and the rate of seedling emergence can beobserved and employed as an index of germination rate and viability. Thetreatment conditions required to obtain significant scarification and/orgermination rate improvement of seeds that have relatively thick, toughhusks and/or hulls are more severe than are the conditions required toachieve similar improvements with seeds that have thinner coverings. Forinstance, higher dosage rates, longer contact times, and/or highercontacting temperatures are required to effect a significant degree ofscarification and/or germination rate improvement with fruit seeds suchas peach and avocado seeds than are required for vegetable, grain andflowering plant seeds such as lettuce, wheat, barley, and ornamentalflower seeds.

The methods of this invention can also be employed to improve theprocessability and/or the digestibility of plant seeds. In particular,these methods can be employed to soften the seed hull or husk or tocompletely remove such seed coverings and thereby simplify subsequentprocessing such as the extraction of oils from oil-containing seeds andthe manufacture of food products for animals including humans.

The production of vegetable oils can be facilitated by contacting theoil-containing seeds with the urea-sulfuric acid component in accordancewith this invention under conditions sufficient to substantially weakenor remove the seed covering. Such contacting conditions are generallymore severe than those required to just remove residual organic matter(although the removal of such organic matter also facilitates andsimplifies the recovery of oil from seeds). Illustrative of suitablecontacting conditions are contact times of at least about 30 minutes,and contacting temperatures of at least about 90° F. Similarimprovements in oil-extractibility can be achieved at lower temperaturesand longer contact times, or, conversely, higher temperatures andshorter contact times. The seed-oil may then be produced by solventextraction and/or expression procedures which are known in the art.Illustrative of vegetable oils the production of which can befacilitated by this invention are sunflower oil, safflower oil, linseedoil, cotton seed oil, peanut oil, perilla oil, oiticica oil, Tung oil,and the like.

The digestibility of plant seeds by all types of animals, includinghumans, can be improved by treating the plant seeds in accordance withthe methods of this invention. Even very mild contacting conditionsimprove the digestibility of plant seeds to a detectable extent. Greaterimprovement in digestibility and food value can be achieved by the useof longer contact times, higher contacting temperatures, and/or higherdosage rates The methods of this invention are particularly suitable forimproving the digestibility and food value of grains such as corn,wheat, rye, barley, and of plant seeds which are customarily used forthe manufacture of animal feeds such as cottonseed which is employed tomanufacture cotton seed meal for cattle and other domestic animals.Seeds which are to be employed in animal feeds can be treated, inaccordance with this embodiment, either as the whole raw seed, or theycan be crushed or subdivided by grinding or milling prior to treatment.Crushed or subdivided seeds have higher surface areas and at leastpartially weakened physical structure, both of which increase the rateat which the seed components can be converted to feeds of improved foodvalue.

Significant improvement in food value can be achieved within the timeframes referred to above. The extent of food value improvement can bedetermined by digestibility tests known to the food processingindustries. For instance, the degree of improvement of ruminant foodvalue can be determined by procedures known to the animal husbandryindustry such as the artificial ruminant study which involves thedetermination of invitro dry matter disappearance (IVDMD) The invitrodry matter disappearance test involves the innoculation of standardnutrient broth containing the treated seeds with rumen microorganisms atstandard pH and temperature for about 12 to 16 hours and determining, byfiltration and drying, the amount of dry matter remaining in thedigested mixture Comparison of that value to the amount of dry matteradded to the nutrient broth establishes the extent to which the treatedseeds have been digested Similar tests are available for determining thefood value of human foods, and the results of such tests can be employedto provide at least a qualitative evaluation of food value for otheranimals as well.

These methods are also useful for improving the processability of plantseeds when it is desired to convert the plant seeds to seed-derivedproducts, and they are particularly useful for the manufacture of grainproducts such as bakery products, flour and other baking materials,cereals and other grain-containing breakfast foods, fast-cooking rice,wheat and other grains, and other seed-derived products. These methodsare also useful for improving the processability of plant seeds for themanufacture of secondary food products such as corn syrup, corn starchand starches derived from other grain crops, and the like. The rate atwhich the improvements in plant seed processability are achieved and,thus, the degree of improvement obtained with any particular combinationof temperature, dosage rate and contact time, can be increased bycrushing and/or subdividing the plant seeds prior to or duringtreatment.

The novel methods of this invention provide expedient procedure forremoving residual organic material from plant seeds, scarifying orotherwise reducing the thickness of and/or increasing the moisturepermeability of seed hulls or husks, increasing seed germination rate,improving seed storage-stability, and improving the processability ofplant seeds for the manufacture of seed-derived products. As onedramatic demonstration of the advantages of this invention, cotton seedscovered with lint can be completely delinted, and their germination ratecan be increased by as much as 20 percent, in a simple batch operationby immersing the seeds in the 17-0-0-17 formulation at ambienttemperature for about one hour.

These methods do not require the use of complex mechanical equipmentsuch as that required for conventional mechanical plant seed scarifyingprocedures. Nor do they require the use and expenditure of substantialquantities of caustic or other reactants. They also do not result in theintroduction of any toxic materials into the treated plant seeds orseed-derived products. On the contrary, these methods introduce nutrientnitrogen and sulfur into the treated seed product, which components areuseful feed supplements for some domestic animals The preferredurea-sulfuric acid components employed in the methods and compositionsof this invention do not contain potentially toxic decompositionproducts of urea and/or sulfuric acid such as sulfamic acid or ammoniumsulfamate and thus do not introduce those materials into the seedproduct or seed-derived products. The methods of this invention alsoprovide the user with considerable flexibility in controlling thequality of the seed product depending upon the contacting temperatures,times and dosage rates employed. Thus, cotton seeds may be treated underconditions which are sufficient only to remove residual lint or, by theuse of more severe contacting conditions, may be converted to a productthat is more easily processed to obtain cotton seed oil and/or toproduce cotton seed-derived food products such as cotton seed meal.Similar results can be achieved with other plant seeds.

The invention is further described by the following examples which areillustrative of specific modes of practicing the invention and are notintended as limiting the scope of the invention as defined by theappended claims.

EXAMPLE I

Cotton seeds, as received from a cotton gin still covered with lint, arecontacted with a urea-sulfuric acid component having the composition10-0-0-18 by immersing the seeds in the urea-sulfuric acid component for40 minutes at 70° F. The treated cotton seeds are then removed from thesolution and washed with water. The treated seeds are completely free ofcotton lint and the surfaces of the seeds appear to be somewhat darkenedtoward brown, apparently due to the removal of a portion of the outerseed coating.

EXAMPLE II

The operation described in Example I is repeated with the exception thatthe lint-containing cotton seeds are treated by immersion in aurea-sulfuric acid component having the formulation 17-0-0-17 at 70° F.for one hour. The treated seeds recovered from the urea-sulfuric acidcomponent are completely free of lint.

EXAMPLE III

The cotton seed treatment described in Example I is repeated with theexception that the lint-containing cotton seeds are treated by immersionin a urea-sulfuric acid mixture having the composition 28-0-0-9 for 3hours at 70° F. Even after such contacting, very little, if any, of thelint is removed from the seeds.

EXAMPLE IV

Quantities of the untreated cotton seeds employed in Examples I, II, andIII, and of the seeds treated in those examples are planted in pottingmix and are maintained in a greenhouse at about 80° F. until germinationoccurs. The untreated cotton seeds germinate and the seedlings breakthrough the soil surface in approximately 5 1/2 days. The seeds treatedin Examples I and II germinate, and essentially all of the seedlingsbreak through the soil surface, at the same time in approximately 4days. Only one seed treated in Example III, out of more than 50 whichare planted, germinates and breaks through the soil surface in twoweeks.

EXAMPLE V

Avocado seeds are scarified by immersing the seeds in urea-sulfuric acidcomponent having the formulation 18-0-0-17 at 90° F. for 90 minutes.

EXAMPLE VI

The processability of sunflower seeds for the subsequent extraction ofthe sunflower seed oil is improved by spraying the seeds with aurea-sulfuric acid component having the formulation 10-0-0-18 at adosage rate corresponding to 5 pounds of the combination of urea andsulfuric acid per 100 pounds of sunflower seeds and maintaining thecoated seeds at 80° F. for 1 hour. The seeds are then washed with waterand are processed by conventional methods to recover sunflower seed oil.

EXAMPLE VII

The processability of raw wheat for the production of wheat flour isimproved by spraying the wheat seeds with a urea-sulfuric acid componenthaving the composition 17-0-0-17 at a dosage rate corresponding to 10pounds of the combination of urea and sulfuric acid per 100 pounds ofraw wheat seeds. The wheat is contacted for 1 hour at 70° F., washedwith water to remove the urea-sulfuric acid component and milled toproduce wheat flour.

EXAMPLE VIII

The germination rate of rice is increased by spraying the rice seedsevenly with a urea-sulfuric acid component having the formulation17-0-0-17 at a dosage rate corresponding to 4 pounds of the combinationof urea and sulfuric acid per 100 pounds of rice seeds, mixing to assureeven distribution of the urea-sulfuric acid component over the riceseeds, and contacting the resulting mixture for 20 minutes at 70° F. Thetreated rice seeds are water washed to remove the urea-sulfuric acidcomponent.

EXAMPLE IX

The storage stability of peach seeds which have residual fruit matter onthe seed hull is improved by spraying the peach seeds with an aqueousurea-sulfuric acid component prepared by diluting 1 volume of 17-0-0-17with 4 volumes of water and applying the resulting solution evenly tothe outer surfaces of the peach seeds at a dosage rate corresponding to2 pounds of the combined weight of urea and sulfuric acid per 100 poundsof peach seeds. The treated seeds are stored without further treatmentor are water washed to remove the urea-sulfuric acid component 1 hourafter application.

While particular embodiments of this invention have been described, itwill be understood, of course, that the invention is not limited theretosince many obvious modifications can be made and it is intended toinclude within this invention any such modifications as will fall withinthe scope of the appended claims.

Having described my invention, I claim:
 1. A composition of mattercomprising a mixture of plant seeds and an aqueous solution comprisingurea and sulfuric acid, in which solution the molar ratio of said ureato said sulfuric acid is within the range of about 1/4 to about 7/4, andwherein said urea and said sulfuric acid, in combination, constitute atleast about 0.5 weight percent of said solution.
 2. A composition ofmatter comprising a mixture of plant seeds and the monourea adduct ofsulfuric acid.
 3. A composition of matter comprising a mixture of plantseeds and the reaction product of urea and sulfuric acid, in whichreaction product the molar ratio of said urea to said sulfuric acid iswithin the range of about 1/2 to about 3/2.
 4. The composition definedin any one of claims 1, 2 or 3 further comprising a surfactant.
 5. Thecomposition defined in any one of claims 1, 2 or 3 free of decompositionproducts of urea and sulfuric acid.
 6. The composition defined in anyone of claims 1, 2 or 3 free of sulfamic acid and ammonium sulfamate. 7.The composition defined in any one of claims 1 or 3 wherein said molarratio of urea to sulfuric acid is at least about
 1. 8. The compositiondefined in any one of claims 1, 2 or 3 wherein the concentration ofequivalent urea and sulfuric acid, in combination, corresponds to atleast about 0.5 pound per 100 pounds of said seeds.
 9. The compositiondefined in any one of claims 1, 2 or 3 wherein the concentration ofequivalent urea and sulfuric acid, in combination, corresponds to atleast about 1 pound per 100 pounds of said seeds.
 10. The compositiondefined in any one of claims 1, 2 or 3 wherein the concentration ofequivalent urea and sulfuric acid, in combination, constitutes at leastabout 5 pounds per 100 pounds of said seeds.
 11. The composition definedin any one of claims 1, 2 or 3 free of sulfamic acid and ammoniumsulfamate, wherein the concentration of equivalent urea and sulfuricacid, in combination corresponds to at least about 1 pound per 100pounds of said seeds.
 12. The composition defined in claim 11 furthercomprising a surfactant.